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  • 1
    In: Environmental Pollution, Elsevier BV, Vol. 263 ( 2020-08), p. 114437-
    Type of Medium: Online Resource
    ISSN: 0269-7491
    RVK:
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2020
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    SSG: 12
    SSG: 14
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  • 2
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 22, No. 18 ( 2022-09-22), p. 12417-12441
    Abstract: Abstract. We carried out a closure study of aerosol–cloud interactions during stratocumulus formation using a large eddy simulation model UCLALES–SALSA (University of California Los Angeles large eddy simulation model–sectional aerosol module for large applications) and observations from the 2020 cloud sampling campaign at Puijo SMEAR IV (Station for Measuring Ecosystem–Atmosphere Relations) in Kuopio, Finland. The unique observational setup combining in situ and cloud remote sensing measurements allowed a closer look into the aerosol size–composition dependence of droplet activation and droplet growth in turbulent boundary layer driven by surface forcing and radiative cooling. UCLALES–SALSA uses spectral bin microphysics for aerosols and hydrometeors, and incorporates a full description of their interactions into the turbulent-convective radiation-dynamical model of stratocumulus. Based on our results, the model successfully described the probability distribution of updraught velocities and consequently the size dependency of aerosol activation into cloud droplets, and further recreated the size distributions for both interstitial aerosol and cloud droplets. This is the first time such a detailed closure is achieved not only accounting for activation of cloud droplets in different updraughts, but also accounting for processes evaporating droplets and drizzle production through coagulation–coalescence. We studied two cases of cloud formation, one diurnal (24 September 2020) and one nocturnal (31 October 2020), with high and low aerosol loadings, respectively. Aerosol number concentrations differ more than 1 order of magnitude between cases and therefore, lead to cloud droplet number concentration (CDNC) values which range from less than 100 cm−3 up to 1000 cm−3. Different aerosol loadings affected supersaturation at the cloud base, and thus the size of aerosol particles activating to cloud droplets. Due to higher CDNC, the mean size of cloud droplets in the diurnal high aerosol case was lower. Thus, droplet evaporation in downdraughts affected more the observed CDNC at Puijo altitude compared to the low aerosol case. In addition, in the low aerosol case, the presence of large aerosol particles in the accumulation mode played a significant role in the droplet spectrum evolution as it promoted the drizzle formation through collision and coalescence processes. Also, during the event, the formation of ice particles was observed due to subzero temperature at the cloud top. Although the modelled number concentration of ice hydrometeors was too low to be directly measured, the retrieval of hydrometeor sedimentation velocities with cloud radar allowed us to assess the realism of modelled ice particles. The studied cases are presented in detail and can be further used by the cloud modellers to test and validate their models in a well-characterized modelling setup. We also provide recommendations on how increasing amount of information on aerosol properties could improve the understanding of processes affecting cloud droplet number and liquid water content in stratiform clouds.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2022
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  • 3
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 16, No. 10 ( 2016-05-27), p. 6495-6509
    Abstract: Abstract. There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from −38 to −10 °C at 5–15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between −39.0 and −37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2016
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  • 4
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 21, No. 3 ( 2021-02-09), p. 1683-1695
    Abstract: Abstract. Long-term statistics of atmospheric aerosol and especially cloud scavenging were studied at the Puijo measurement station in Kuopio, Finland, during October 2010–November 2014. Aerosol size distributions, scattering coefficients at three different wavelengths (450, 550, and 700 nm), and absorption coefficient at wavelength 637 nm were measured with a special inlet system to sample interstitial and total aerosol in clouds. On average, accumulation mode particle concentration was found to be correlated with temperature with the lowest average concentrations of 200 cm−3 around 0 ∘C increasing to 800 cm−3 at 20 ∘C. The scavenging efficiencies of both scattering and absorbing material were observed to have a slightly positive temperature correlation in in-cloud measurements. At 0 ∘C, the scavenging efficiencies of scattering and absorbing material were 0.85 and 0.55 with slopes of 0.005 and 0.003 ∘C−1, respectively. Scavenging efficiencies were also studied as a function of the diameter at which half of the particles are activated into cloud droplets. This analysis indicated that there is a higher fraction of absorbing material, typically black carbon, in smaller sizes so that at least 20 %–30 % of interstitial particles within clouds consist of absorbing material. In addition, the PM1 inlet revealed that approximately 20 % of absorbing material was observed to reside in particles with ambient diameter larger than ∼ 1 µm at relative humidity below 90 %. Similarly, 40 % of scattering material was seen to be in particles larger than 1 µm. Altogether, this dataset provides information on the size-dependent aerosol composition and in-cloud scavenging of different types of aerosol. The dataset can be useful in evaluating how well the size-dependent aerosol composition is simulated in global aerosol models and how well these models capture the in-cloud scavenging of different types of aerosol in stratus clouds.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2021
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  • 5
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 21, No. 24 ( 2021-12-17), p. 18283-18302
    Abstract: Abstract. Efforts have been spent on investigating the isothermal evaporation of α-pinene secondary organic aerosol (SOA) particles at ranges of conditions and decoupling the impacts of viscosity and volatility on evaporation. However, little is known about the evaporation behavior of SOA particles from biogenic organic compounds other than α-pinene. In this study, we investigated the isothermal evaporation behavior of the α-pinene and sesquiterpene mixture (SQTmix) SOA particles under a series of relative humidity (RH) conditions. With a set of in situ instruments, we monitored the evolution of particle size, volatility, and composition during evaporation. Our finding demonstrates that the SQTmix SOA particles evaporated slower than the α-pinene ones at any set of RH (expressed with the volume fraction remaining, VFR), which is primarily due to their lower volatility and possibly aided by higher viscosity under dry conditions. We further applied positive matrix factorization (PMF) to the thermal desorption data containing volatility and composition information. Analyzing the net change ratios (NCRs) of each PMF-resolved factor, we can quantitatively compare how each sample factor evolves with increasing evaporation time or RH. When sufficient particulate water content was present in either SOA system, the most volatile sample factor was primarily lost via evaporation, and changes in the other sample factors were mainly governed by aqueous-phase processes. The evolution of each sample factor of the SQTmix SOA particles was controlled by a single type of process, whereas for the α-pinene SOA particles it was regulated by multiple processes. As indicated by the coevolution of VFR and NCR, the effect of aqueous-phase processes could vary from one to another according to particle type, sample factors, and evaporation timescale.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2021
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  • 6
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 20, No. 20 ( 2020-10-20), p. 11809-11821
    Abstract: Abstract. Nucleation of atmospheric vapours produces more than half of global cloud condensation nuclei and so has an important influence on climate. Recent studies show that monoterpene (C10H16) oxidation yields highly oxygenated products that can nucleate with or without sulfuric acid. Monoterpenes are emitted mainly by trees, frequently together with isoprene (C5H8), which has the highest global emission of all organic vapours. Previous studies have shown that isoprene suppresses new-particle formation from monoterpenes, but the cause of this suppression is under debate. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we show that isoprene reduces the yield of highly oxygenated dimers with 19 or 20 carbon atoms – which drive particle nucleation and early growth – while increasing the production of dimers with 14 or 15 carbon atoms. The dimers (termed C20 and C15, respectively) are produced by termination reactions between pairs of peroxy radicals (RO2⚫) arising from monoterpenes or isoprene. Compared with pure monoterpene conditions, isoprene reduces nucleation rates at 1.7 nm (depending on the isoprene ∕ monoterpene ratio) and approximately halves particle growth rates between 1.3 and 3.2 nm. However, above 3.2 nm, C15 dimers contribute to secondary organic aerosol, and the growth rates are unaffected by isoprene. We further show that increased hydroxyl radical (OH⚫) reduces particle formation in our chemical system rather than enhances it as previously proposed, since it increases isoprene-derived RO2⚫ radicals that reduce C20 formation. RO2⚫ termination emerges as the critical step that determines the highly oxygenated organic molecule (HOM) distribution and the corresponding nucleation capability. Species that reduce the C20 yield, such as NO, HO2 and as we show isoprene, can thus effectively reduce biogenic nucleation and early growth. Therefore the formation rate of organic aerosol in a particular region of the atmosphere under study will vary according to the precise ambient conditions.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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  • 7
    Online Resource
    Online Resource
    Copernicus GmbH ; 2020
    In:  Atmospheric Chemistry and Physics Vol. 20, No. 22 ( 2020-11-27), p. 14393-14405
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 20, No. 22 ( 2020-11-27), p. 14393-14405
    Abstract: Abstract. Ammonia (NH3), a gaseous compound ubiquitously present in the atmosphere, is involved in the formation of secondary organic aerosol (SOA), but the exact mechanism is still not well known. This study presents the results of SOA experiments from the photooxidation of α-pinene in the presence of NH3 in the reaction chamber. SOA was formed in in nucleation experiments and in seeded experiments with ammonium sulfate particles as seeds. The chemical composition and time series of compounds in the gas and particle phase were characterized by an online high-resolution time-of-flight proton-transfer-reaction mass spectrometer (HR-ToF-PTRMS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. Our results show that the mass concentration of ammonium (NH4+) was still rising even after the mass concentration of the organic component started to decrease due to aerosol wall deposition and evaporation, implying the continuous new formation of particle-phase ammonium in the process. Stoichiometric neutralization analysis of aerosol indicates that organic acids have a central role in the formation of particle-phase ammonium. Our measurements show a good correlation between the gas-phase organic mono- and dicarboxylic acids formed in the photooxidation of α-pinene and the ammonium in the particle phase, thus highlighting the contribution of gas-phase organic acids to the ammonium formation. The work shows that the gas-phase organic acids contribute to the SOA formation by forming organic ammonium salts through acid–base reaction. The changes in aerosol mass, particle size and chemical composition resulting from the NH3–SOA interaction can potentially alter the aerosol direct and indirect forcing and therefore alter its impact on climate change.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
    detail.hit.zdb_id: 2092549-9
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  • 8
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 22, No. 8 ( 2022-04-19), p. 5117-5145
    Abstract: Abstract. The formation of ice particles in Earth's atmosphere strongly influences the dynamics and optical properties of clouds and their impacts on the climate system. Ice formation in clouds is often triggered heterogeneously by ice-nucleating particles (INPs) that represent a very low number of particles in the atmosphere. To date, many sources of INPs, such as mineral and soil dust, have been investigated and identified in the low and mid latitudes. Although less is known about the sources of ice nucleation at high latitudes, efforts have been made to identify the sources of INPs in the Arctic and boreal environments. In this study, we investigate the INP emission potential from high-latitude boreal forests in the mixed-phase cloud regime. We introduce the HyICE-2018 measurement campaign conducted in the boreal forest of Hyytiälä, Finland, between February and June 2018. The campaign utilized the infrastructure of the Station for Measuring Ecosystem-Atmosphere Relations (SMEAR) II, with additional INP instruments, including the Portable Ice Nucleation Chamber I and II (PINC and PINCii), the SPectrometer for Ice Nuclei (SPIN), the Portable Ice Nucleation Experiment (PINE), the Ice Nucleation SpEctrometer of the Karlsruhe Institute of Technology (INSEKT) and the Microlitre Nucleation by Immersed Particle Instrument (µL-NIPI), used to quantify the INP concentrations and sources in the boreal environment. In this contribution, we describe the measurement infrastructure and operating procedures during HyICE-2018, and we report results from specific time periods where INP instruments were run in parallel for inter-comparison purposes. Our results show that the suite of instruments deployed during HyICE-2018 reports consistent results and therefore lays the foundation for forthcoming results to be considered holistically. In addition, we compare measured INP concentrations to INP parameterizations, and we observe good agreement with the Tobo et al. (2013) parameterization developed from measurements conducted in a ponderosa pine forest ecosystem in Colorado, USA.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2022
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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  • 9
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 16, No. 21 ( 2016-11-03), p. 13601-13618
    Abstract: Abstract. New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2016
    detail.hit.zdb_id: 2092549-9
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  • 10
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 20, No. 13 ( 2020-07-02), p. 7693-7716
    Abstract: Abstract. The measurements of aerosol particles with a filter inlet for gases and aerosols (FIGAERO) together with a chemical ionisation mass spectrometer (CIMS) yield the overall chemical composition of the particle phase. In addition, the thermal desorption profiles obtained for each detected ion composition contain information about the volatility of the detected compounds, which is an important property for understanding many physical properties like gas–particle partitioning. We coupled this thermal desorption method with isothermal evaporation prior to the sample collection to investigate the chemical composition changes during isothermal particle evaporation and particulate-water-driven chemical reactions in α-pinene secondary organic aerosol (SOA) of three different oxidative states. The thermal desorption profiles of all detected elemental compositions were then analysed with positive matrix factorisation (PMF) to identify the drivers of the chemical composition changes observed during isothermal evaporation. The keys to this analysis were to use the error matrix as a tool to weight the parts of the data carrying most information (i.e. the peak area of each thermogram) and to run PMF on a combined data set of multiple thermograms from different experiments to enable a direct comparison of the individual factors between separate measurements. The PMF was able to identify instrument background factors and separate them from the part of the data containing particle desorption information. Additionally, PMF allowed us to separate the direct desorption of compounds detected at a specific elemental composition from other signals with the same composition that stem from the thermal decomposition of thermally instable compounds with lower volatility. For each SOA type, 7–9 factors were needed to explain the observed thermogram behaviour. The contribution of the factors depended on the prior isothermal evaporation. Decreased contributions from the factors with the lowest desorption temperatures were observed with increasing isothermal evaporation time. Thus, the factors identified by PMF could be interpreted as volatility classes. The composition changes in the particles due to isothermal evaporation could be attributed to the removal of volatile factors with very little change in the desorption profiles of the individual factors (i.e. in the respective temperatures of peak desorption, Tmax). When aqueous-phase reactions took place, PMF was able to identify a new factor that directly identified the ions affected by the chemical processes. We conducted a PMF analysis of the FIGAERO–CIMS thermal desorption data for the first time using laboratory-generated SOA particles. But this method can be applied to, for example, ambient FIGAERO–CIMS measurements as well. There, the PMF analysis of the thermal desorption data identifies organic aerosol (OA) sources (such as biomass burning or oxidation of different precursors) and types, e.g. hydrocarbon-like (HOA) or oxygenated organic aerosol (OOA). This information could also be obtained with the traditional approach, namely the PMF analysis of the mass spectra data integrated for each thermogram. But only our method can also obtain the volatility information for each OA source and type. Additionally, we can identify the contribution of thermal decomposition to the overall signal.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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